O-acylbenzohydorxamates

ABSTRACT

The compound having formula;   WHEREIN, R represents alkyl having one to six carbon atoms and X represents hydrogen, halogen, alkyl having one to three carbon atoms or alkoxy having one to three carbon atoms and n is an integer of 0-5 prepared in accordance with the following equation:   WHEREIN M represents hydrogen or metal atom and m represents valency of M and R, X and n, each have the aforesaid meanings. The novel compounds have superior acaricidal activities without mammalian toxicity.

Unit ti Sites aient [72] Inventors Teruhisa Noguchi Fujisawa-shi; Mitsuo Asada, Naita-gun; Reiji Sakimoto, Taitaoka-shi; Yoshiyasu Aolki, lKaminikawa-gun; Miitio Sawalki, Taitaoitashi, all of Japan [2]] Appl. No. 723,652 22 Filed Apr. 24, 1968 [45] Patented Dec. 7, 1971 [73] Assignee Nippon Soda Kabushiki Kaisha Tokyo-to, J apart [32] Priorities May 2, 1967 [33] Japan [31] 42/27706;

Nov. 30, 1967, Japan, No. 42/76 138 [54] O-AQYLBENZOHYDORXAMATES 9 Claims, 6 Drawing Figs.

[52] 11.8. C1 260/471R, 260/453 R, 260/473 R. 260/477, 424/309 [51] Int. 4C1 .t C07c 93/00 [50] Field of Search 260/477, 471R, 473, 453, 476, 473 S [56] References Cited UNITED STATES PATENTS 3.032555 5/[962 Oxiey et a] 260/476 2.097.136 l0/l937 Smith et a] 260/476 453,035 5/l89l Bongartz 260/476 FOREIGN PATENTS 979,562 H1965 Great Britain 260/477 OTHER REFERENCES Unite Processes in Organic Synthesis, P. H. Groggins. 5th Edition, P. 7 l 7 Primary E.raminer- Lorraine A. Weinberger Ass-[slam Examiner-Jacqueline Davison Almrney-Nolte and Noite ABSTRACT: The compound having formula:

wherein M represents hydrogen or metal atom and m represents valency of M and R. X and n. each have the aforesaid meanings The novel compounds have superior acaricidai activities without mammalian toxicity.

O-ACYLBENZOIIYDORXAMATIES THE DETAILED EXPLANATION OF THE INVENTION This invention relates to novel O-acylbenzohydroxamates having acaricidal activity and to a novel process for the preparation of the same.

The novel compounds in the present invention are characterized by the formula (I) O1 OOHs 0. (Lag wherein M represents hydrogen or metal atom and m represents valency of M and R, X and n each have the aforesaid meanings.

Usually the process of the invention is carried out in a suita ble inert solvent at a temperature of about -20l00 C. and the reaction is completed in between 2 hours and hours.

In the case where the calcium, silver, zinc, copper (cuprous, cupric) or iron (ferrous, ferric) salt of compound II is used, the reaction is preferably carried out in low polar solvent such as benzene, toluene, xylene or tetrachloromethane at a temperature of about l00 C.

Further, when an alkali metal salt such as a sodium or potassium salt of compound (II) is employed in the reaction, high polar solvent such as acetone, methylethylketone, cyclohexanone, acetonitrile or tetrahydrofuran is preferably employed at a temperature of about 20-0 C.

When an alkylhydroxamate is used as the starting material, the reaction can be promoted at a temperature of about 20 -0 C. by use of a base such as sodium hydroxide. Water has a tendency to decrease the yield of the products (I), so generally the introduction of water into the reaction mixture is to be avoided, however, if necessary, the minimum quantity of water may be used, for example, if necessary to dissolve the alkali metal hydroxide, a small portion of water may be added.

Furthermore a little amount of an amino compound such as triethyl amine can be added as a catalyst.

After the reaction is terminated, the products (I) are isolated from the reaction mixture by employing the well-known procedures. For example, in case of the reaction in a non or low polar solvent, after filtering off the metal chloride crystals present, sodium hydroxide is added to the filtrate and unreacted starting materials and by-products of the organic acids present are extracted into the sodium hydroxide layer. The upper solvent layer is separated off and dried, and the solvent is distilled off. The product (I) is obtained in the form of crystals or oil, having a high degree of purity more than percent, about 20 percent or less of impurity is an N-acyl compound which is a main byproduct.

The product (I) has geometrical isomers which can be distinguished by their Infrared Spectrum absorptions. The ratio of the various isomers depends the reaction conditions.

One isomer has been named the a-isomer" and the other the B-isomer" in consideration of different physical properties and observation of Infrared Spectrum absorption in the position of 9,41. wavelength. FIG. 1-6 show the Infrared Spectrum absorptions of the product (I) in tetrachloromethane. FIG. I shows the a-isomer and FIG. 2 shows the B-isomer of compound No. in Table I. FIG. 3 is the infrared absorption spectrum of an a-isomer and FIG. d of the B-isomer of compound No. 6 in the same table. FIG. 5 shows the spectrum of the a-isomer and FIG. 4 the ,B-isomer of compound No. 7 in the table.

In order to facilitate a clear understanding of the invention, the following preferred specific embodiments are described.

EXAMPLE I preparation of Cl (|)CH A. To a suspension of 70 g. (0.188 mole) of a silver salt of ethyl 3,6-dichloro-2-methoxybenzohydroxamate in 350 ml. of benzene, toluylchloride 29 g. (0. H38 mole) was added and the mixture stirred at about 50 C. for 6 hours.

After termination of the reaction, silver chloride was filtered off and the filtrate was washed with ml. of 2 percent sodium hydroxide aqueous solution to remove the impurities and then washed with water and dried.

The resulting benzene solution was distilled to remove benzene and 69.2 g. of oily matter (consists of a-isomer and a little amount of byproduct of N-acyl compounds) were obtained as the residue.

The oily matter is gradually crystallized at room temperature, and the crystals were recrystallized from ligroin-petroleum ether to obtain the pure crystals of a-isomer, m.p. 825- 83.5 C. B. A mixture of 88.5 g. (0.3 mole) of copper salt of ethyl 2,6- dichloro-2-methoxybenzohydroxamate and 42 g. (0.3 mole) of toluylchloride in 800 ml. of benzene was stirred at 50 C. for 4 hours. 90 g. of oily matter substantially consisting of ,8- isomer were obtained after a working up similar to example 1 (A). The recovered product was purified by chromatography on silica gel column using acetone-n-hexane as eluent to obtain pure crystals, of B-isomer m.p. 37 38 C.

EXAMPLE 2 preparation of Cl OCH To a solution of 10.6 g. (0.04 mole) ethyl 3,6-dichloro-2- methoxybcnzohydroxamate and 6.2 g. (0.04 mole) of toluylchloride, 6.2 g. in ml. of acetone cooled at l0 C., 6 ml. (0.04 mole) of 30 percent sodium hydroxide aqueous solution was added in dropwise fashion for about a half hour and the mixture was stirred for 2 more hours at the same temperature.

After the termination of the reaction, the temperature was gradually raised to room temperature and then the acetone 5 was distilled off.

Forty ml. of chloroform and 20 ml. of 2 percent sodium hydroxide aqueous solution were added to the residue and the resulting mixture was shaken whereby the byproduct was extracted into the water layer. The chloroform layer was evaporated to obtain g. of oily matter comprising mainly the B-isomer of ethyl0-toluyl-3,6-dichloro-2-methoxybenzohydroxamate and a little amount (about 7 percent) of byproduct (N-acyl compound).

(IJCH 10.6 g (0.04 mole) of ethyl 3,6-dichloro-2-n1cthoxybenzohydroxamate, 6.2 g

l0.6 g. (0.04 mole) of ethyl 3,6-dichloro-2-methoxybenzohydroxamate, 6.2 g. (0.04 mole) of toluylchloride and 0.35 mg. of treithylamine (catalyst) were dissolved into 250 ml. of chloroform. To the solution cooled to about 0 C., 6 ml. (0.04 mole) of percent sodium hydroxide aqueous solution was gradually added for about 15 minutes and themixture was stirred for 2 hours at the same temperature. After the termination of the reaction, the temperature was gradually raised to room temperature. The chloroform layer was washed with 20 ml. of 2 percent sodium hydroxide aqueous solution in order to remove byproduct and washed with water and dried.

The resultant chloroform solution was evaporated to obtain an oily residue comprising mainly the a-isomer, of ethyl-0- toluyl-3,6-dichloro-2-methoxy hydroxamate m.p. 82.583.5 C. and a little amount (about 8 percent) of byproduct N-acyl compound.

in addition to the above mentioned compounds described in the preceding examples, some typical compounds of the present invention are listed in table I.

These examples and table I include merely some of the compounds of the present invention, so that the scope of the present invention is not limited only to those compounds listed in table 1.

TABLE I M.P. or refractive index No. of a-isomer, fl-isomer, compound Chemical structure Chemical name 0. C.

1 C1 0 CH Methyl O-benzoyl-3,6- 99-100 dichloro-Z-methoxybenzohydroxamate. (IJ=NO CH 51 WQ 2 C1 0 OH; Methyl 0-toluyl-3,6- 98-99 dlchloro-Z-methoxybenzohydroxamate. C|3=N-O CH 3 C1 0 CH Methyl 0-(4-ch1oro- 104-105 benzoyl)-3,6-dichloro-2- methoxydenzo- (IJ=NO CH3 hydroxamate.

4 Cl 0 CH Methyl O-(4-nltro- 109-110 benzoyl)-3,6-dlchl0ro-2- methoxybenzo- C|7=NO CH3 hydroxamate. l 01 O 5 Cl 0 O H; Ethyl O-benzoyl-3,6- 87-88 -71 dichloro-Z-methoxybcnzohydrox amate. T=N-O C2H 6 Cl 0 CH; Ethyl 0-(3 6-dlchloro-2- 84-85. 5 05-96 I methoxybenz0yl)-3,6-

dichloro-2-methoxy- C=N O O 1H5 benzohydroxamate.

TABLE I -(ontinued M.P. or refractive lndex N o. of a-isomer, B-isomer, compound Chemical structure Chemical name C. C.

7 Cl OCH; Ethyl O-toluyl-3,6- 82. 5-83. 5 37-38 dichloro-Z-mcthoxybenxohydroxamate. ('3=NO 0211 01 r@- 8 Cl OCH Ethyl O-(4-ch1oro- 70-71 benmyD-Bfi'dichlorohydroxamate. (|3=N-O C211 l rQ l Crude product viscous oil.

It is the advantages of the invention that the compounds listed in table I possess acan'cidal activity and have no phytotoxicity. Usually, a small but effective amount of the compounds are applied at a concentration of 0.0125 to 0.05 percent on plants to combat and eradicate the pests. The concentrations of the active compounds in the compositions are varied by kinds of the formulation used, they may be used in a range of l0-8O percent, preferably 20-60 percent in the wettable powder, -50 percent, more preferably -40 percent in the emulsifiable concentrate and l-l0 percent in the dust. The nonlimiting example of the composition of the invention are illustrated as follows:

Example 4: Wettable powder Parts by weight Compound 5 20 Higher alcoholsulfonates 5 Diatomaceous earth 75 These were mixed and micronized in jet pulverizer to a particle size of 4-20 micron.

In practical use, the micronized mixture was diluted with water in a concentration of 0.01 to 0.05 percent of active ingredient water. The suspension was applied as a spray.

Example 5: Emulsifiuhle concentrate Parts by weight C om pou nd 7 Alkylarylpolyoxyethylcne 7 Dimethylformamide 45 Toluene 40 These were mixed and dissolved. in practical use, this solution was diluted with water in a concentration of 0.01 to 0.05 percent of active ingredient and this suspension was sprayed.

Example 6: Dust formulation Parts by weight Compound 5 5 Alkylarylpolyoxyethylene 0.l Talc 94.9

EXAMPLE 7 Acaricidal activity for 2,4,5,4-tetrachlor0 diphenyl sulfone resistant citrus red mite are shown in table ll.

Mandarin orange leaves, on which the living adult female mites (Panonychus citri) were laid, were put into petri dishes, the dead mites were removed after one day of treatment with a water suspension containing 0.05 percent of the compound formulated in emulsifiable concentrate by spraying. After 3 days of spraying, adult mortalities were counted, and the surviving adult mites were removed. The viability of eggs deposited during this period was examined after 15 days of the removal of the surviving adult mites.

Mortality (percent) fi- 11: numbers of living mites in untreated plots b: number of surviving mites in treated plots i-1V) ()vlcldal act1v1ty (percent): X100 a: numbers of eggs deposited. 1): numbers of hatched eggs TAB LE II Adult Ovicidal mortality activity (percent) (percent) No. of compound:

Phenkapton (control) EXAMPLE 8 TABLE III Content of Residual effect compound in (percent) alter suspension (percent) 4 days 23 days N o. of compound:

5 0. 03 100 100 0.015 100 100 7 0. 03 100 100 0.015 100 100 1,1-bis(p-chlorophenyl)-2,2,2-trichloromethanol (control) A We claim: 5. A compound according to claim 1 having the formula I. An O-acylbenzohydroxamate compound of the formula:

c1 OCH:

01 OCH; (]:=N-0om X 6. A compound according to claim 1 having the formula Cl 0 CH wherein, R represents alkyl having one to six carbon atoms CZNMOOH and X,, X and X each represent a member selected from the group consisting of hydrogen, halogen, N0 alkyl having one to three carbon atoms or alkoxy having one to three carbon atoms.

2. A compound according to claim I having the formula 01 OCH:

7. The compound of the formula:

3. A compound according to claim 1 having the formula 8. The compound of the formula:

Cl OCH3 I c1 OCH;

-C=N-OCH:

I I -C=NOC2Hs Cl oc-om I 1 o1 OCO O 4. A compound according to claim 1 having the formula 9. The compound of the formula: C (BCHa Cl ()OHa 40 C=NOC=H5 

2. A compound according to claim 1 having the formula 